Three-phase emulsion of artificial resins



impregnation or matt effects which are fast to washing. The feel of the fabric after treatment by the present process is primarily determined by the quantity of dry substance per unit of surface, which may be relatively high when paste-like preparations are used, but may be almost imperceptible in the case of treatment with diluted baths. On the other hand, the uniformity of the coating or impregnation eect produced is often of decisive importance.

It is known that pigment suspensions, which are applied on the foulard as dye liquors, are inclined to lead easily to so-called migrating which may cause objectionable spots, streaks, etc. after drying. Attempts have been made to reduce or avoid this defect by the addition of small quantities of thickening agents such, for example, as tragacanth, to the foulard liquor. Printing colors which are to be used for machine printing or screen printing must have a considerably higher viscosity than foulard liquors, and therefore require a larger addition of thickening agent.

The artificial resin emulsions described above full to a very great extent the viscosity requirements of pigment dyeing and printing preparations, but printing pastes prepared therewith are suitable for textile printing only in exceptional cases, because they have too high a content of dry substance. rIhe prints produced therewith generally impart a rough and stili feel to the textile fabric after hardening of the artificial resin. If the content of dry substance in the emulsion is lowered to a degree which is no longer harmful by the addition of water, there is obtained a thinly liquid preparation which, without the addition of further thickening agent, can hardly be used for dyeing on a foulard and still less for printing. Accordingly, the problem remains of thickening aqueous thinly liquid preparations without also increasing their content of dry substance.

It is known from U. S. Patent No. 2,361,277 that a thickening effect can be achieved with the emulsions of the oil-in-water type described therein, which contain the articial resin in the aqueous phase, by incorporating in said single aqueous phase by emulsification an organic solvent which is immiscible with water. In contradistinction to increasing the viscosity of aqueous liquids by dissolving colloidal substances therein, such as tragacanth,l starch, methyl-cellulose, polyvinyl alcohol or the like, the methods of the aforesaid patent, which may be called emulsionthickening, enables preparations to be obtained which are very suitable for the improving processes referred to above, and of which the content of dry substance can, if desired, be brought to a few parts per cent. so that unfavorable effects on fabrics due to adhesion, hardening etc., are

` avoided.

The present invention is based on the observation that this emulsion-thickening principle is also of advantage in connection with the emulsions of the aforesaid U. S. Patent No. 2,586,098, filed November 3, 1947, which are of the oil-inwater type and of which the artificial resin is present in the oily phase.

Accordingly, the present invention provides a process for making new three-phase emulsions of artificial resins, more especially suitable for improving textiles, from a two-phase emulsion of which the external aqueous phase consists of a solution containing at least one protein and at least one hydrotropic carbamide capablev of forming a hardenable aminoplast with formaldehyde,

4 and of which the internal oily phase consists of a solution in a substantially water-immiscible organic solvent of a water-insoluble hardenable condensate of formaldehyde with a substance of amide character capable of forming with formaldehyde a hardenable aminoplast and with an alcohol which is substantially immiscible with water, wherein there is incorporated in the emulsion as a second internal oily phase an inert water-immiscible organic solvent having a boiling point which is not appreciably below C. and not appreciably above 200 C.

It is surprising that in the emulsification of an organic solvent in the aforesaid preparations, which are usually previously diluted with water, the primary artificial resin emulsion is not disturbed, so that homogeneous and very stable systems are obtained. The emulsifying and dispersing properties of the aqueous phase appear to suffice for stabilisingv the resin-emulsion and the solvent-emulsion. This applies not only in the case where the additional solvent to be emul- Sified is miscible with the primarily emulsified artificial resin or the solution thereof. The same effect is obtained when a solvent is used which would cause turbidity due to the flocculation of the resin if it were added to the artificial resin solution. The use of solvents which are immiscible or at most miscible to a limited extent with the primarily emulsied artificial resin or its solution constitutes an advantageous form of the process. It must therefore be assumed that the two oily phases, namely the carbamide resin dissolved preferably in an excess of the etherifying agent and the organic solvent which is usually emulsified subsequently, form disperse systems which are substantially independent of one another. Consequently, there are obtained 3-phase emulsions, in which the aqueous solution of the protein containing a hydrotropic carbamide forms the external phase, the artificial resin dissolved in an organic solvent forms the first internal phase, and a water-immiscible solvent, which is usually such as evaporates without leaving any residue, forms the second internal phase.

In order to produce these new preparations which are especially suitable for the application of pigments as referred to above the procedure will generally be first to dilute a carbamide resin emulsion of the kind hereinbefore referred to with water until there is obtained a preparation which after emulsifying therein a certain quantity of an inert water-immiscible organic solvent has the consistency and lcontent of dry substance required for the application in question.

There have been found especially suitable for incorporation in the emulsions as solvents those of a benzine character consisting predominantly of hydrocarbons of the aliphatic series, for example, so-called extraction benzine or heavy benzine, lacquer benzine, sangajol or the like, which generally have no solvent action on carbamide resins of the urea series. It will be understood, of course, that other solvents or mixtures of solvents may be used for example, benzene, chlorobenzene, toluene, xylene, solvent naphtha, tetralin, dipentene, turpentine, trichlorethylene or the like, substances of the aromatic series, beingl however, less favorable from the point of view of hygiene and economy. In principle, however, any desired water-immiscible solvent may be used, provided that it is inert towards the other constituents of the emulsion, that is to say, it undergoes no chemical reaction therewith. Furthermore. there are preferred those solvents of whahaha 134.11111@y points are,notarpreciablybelow 10Q? o; ami no tjapppeoiabiy above. 200 c., ana'- Whh., are therefore neither too. easily volatile nor too, sparingly Volatile,

The;` emulsification ofY the solvent may, be, brought about by means ofthev usualeznulsifying apparatus orstirring4 devices. As. a rule, the

carbamide resin emulsion is previously diluted.V

with Water` andthe solvent',- forming the second disperse.,l phase added gradually, y or if desired,

all. y at once,V DependingV onV the,- relativeA proportionsrof the threephases there are. obtained salvelike-.thiclftlylor` thinly` viscous .Y preparations which have, remarkable stability.v and., keepingT qualities..

While it iis 4of advantageto. use as-the second.

disperse. phase one. Which-A evaporates without. leaving any. residue, therenmy`v be addedA to the` aqueous. protein solution ,serving as the. external phase various,A further,- substances. which` render thapreparation suitable` forl improving fibrous- Eample; 1

1i),` parts `of titanium white are ,nel'y dispersed inL Gifparts otra solutiongconsisting, of' 10 parts` of.l acid casein-..1 partA ofpborax and 391 parts or 8. parts. ofV thiourea are` added'tothe resulting pigment paste'.

Wateriby trituratingy inza disc mill.

and .thereareemulsied thereinii)4 parts of a resin solution consisting.` of' 36 per` cent;` of aU ureathiourea. formaldehyde Ycyclohexanol condensate and 64 per cent. of cyclohexanol.. The resin emulsioneishomogenised in a suitable apparatus, thenv mixed with 292 parts of Water, and 600 parts of lacquer: benzene-(boiling at 150- 20 0` Cj.) are emulsied in the diluted resin emulsion to: form the second'disperse;pha$e., Al though the resin as such is almost "completely in"- soluble in lacquerabenzine, there is obtained 'a smooth fhOmOgeneOuS liqur'vofff-low viscosity and f good.; keeping qualities.

VVA@ lustrous viscose fabric is treated Withthe above liquor, on a foulard and, after being1 dried, is heatedlfor 1/2 hour longerat1130 C., whereby @matt-.effect is obtainedl which Ais;.fast to iWash'-, maand, only Slightly. stifensffthe,ffaloria 5 parts of an-iron-oxidepigmenteare added to 20l parts dof water in which have been dissolved 10,partsi of gelatine, 8 parts'gofurea and Z'parts of thiourea, and the mixture is' triturated" in a roller mill toiformaaiineipastei.k 34y parts of a solutionofper cent. strength of aurea-formaldehyde-butanol iresinfinfbutanol aref-emulsiedingf themas,anda,theiresultina,emulsioniisimixed with 1`part of ammonium formate and figparts;

of Water, whereby a thinly fluid suspension is obtained. The latter is then thickened by the gradual introduction and continuous emulsification of 600" parts. or? :'cylern-z` so? asi to* obtain. a* thinly,- viscous paste.. u

A` cotton fabric. is impregnated* completely 'unil formly-` on the foulardf with' the. resulting', paste'. After dryingthe,fabric,it`is heated .for 1" minute at 170 Ci whereby, the dressingfandlthe coloring'` effect sim'ultaneouslyy produced are xedvery -fas'tl to, Washingand rubbing. Tli'elrelat'ivelylow con'- tenti of'A dry. substanceiintlie preparation used ensures,- that. the. fabric. is. not. substantially. stiiened.

. Efcample V3 43.5 parts of acid casein, 29.25 parts of urea and' 2125f-partsfoff ammoniuifcarbonate'iare di'sf solvedin- 75`^lpartslof' Wateri I'lere are em'ul'sf fied in the`l resulting viscoussol'toi by 'inea 'f1 ofa suitable* a1ipana'itu's`- 60A parts "o'f'f'a condensate* oi urea,l `formald'eliy'deA and butanol;` v'vliicll'A is dis@ solved in- 40-` parts obutemolif The resulting? thick transparent s'alvis dilutedf With-212205 partst of *'water, and thereA1 are"adde`d 1-50'- parts 'of-'f an` aqueous pigmentV slispensioni` whichcontair'1s,in-I additionV ifo-37.5" parts-'of Aan extremel'yifinelyr` di'-v vided' reaction product -1 ofi diazotisedw 2 i 5-dichlor= aniline with 2: 3-h'ydroxynaphtlioic acid-Zf-anisd Y idide 12- parts ofacid casein; Y lpart'siofQ 'boraxf and 5 vparts of` highlyfsulfonat'ed castor oil.I Aft'ri 10 partsof'r ethylene glycol f and ZOpartslori an?- aqueous solutionvr of' 50` 'per-cent` ystrength*of ar'nf monium thiocyanate have -beencaddedfthererare'f emulsiied in the diluted-*and pigmentedl're'sin'f emulsion 350 parts of benzine boilingfai'flOOilillo i C., in which the i primarily emuls'iied-'resiifis` practically insoluble:

There is obtained asmoothfvisco'u'si printing r color `Whiclr isf-printed on a-'crepe*"-fabric off'cotton, viscose or staple lfibersof* regenerated" cella-*1 lose; vAfterffdrying and-"-hamening,forfexample for 5 minutes at 15`O"'C;there are obtained brightprints which are fast to washingfand-rubbingland donotl markedlyl stiften theabicf monia .solution-f of zfpenzcentif strength,',30i parts f ofsureaand 10Tpartsiofatliioureai'inllovpartsmfl water.. 104 parts of'glycerine .are added to tliepigfment` paste, andltherev` are .erulsiedqtherein-: partsiof a melamine-,resinv etheriedfwith butanol anddissolved in 24zparts of;butanol.:v The-Whole isfY then diluted with'jr232 partsof" water, and-the? resulting thinlyr flui-dffsuspension-n isfthen thickened: togiveita-consistencyrsuitable forfprintingw;

The resulting;v thickly viscous :f .printing v, `color has a* content ot 'f dry substancefamounting .only to 17 per cent., andf-.thereforedoes'not substantially-stiien the fabric. When printed onfcotton'l or.- cellulose acetate artificiali-'silk4 and: lhard- A ene.dfor.21/2 minutes-iat 160? Cablackrprintsfast to. washing; are.v obtained.

' Erampl parts, of ther ureaf-frmaldehydeebutanoli resin dissolved in butanol, mentionedfin .Emana-.- ple l3, are emulsied iniasolution `containing partsof casein, 2 parts of'an aqueoussolutionof. sodium Vhydroxide of 30. per.y cent. strength, 20

parts of\-urea,-113 partsv of..Waterf,1.4-parts of av highly -sulphonated--` castor.:` oil, .anda 10 partsaofi. finely dispersed Indanthrene Blue RS (Color Index No. 1106). The resin emulsion is then diluted with a solution of 5 parts oi?4 ammonium chloride in 96 parts of Water, and 500 parts of chlorobenzene are dispersed in the aqueous phase to form the second oily phase. The preparation is treated in a homogeniser and then there are added 150 parts of a neutral emulsion of 30 per cent, strength obtained by polymerising a mixture of acrylic acid ethyl ester and acrylic acid butyl ester Yin aqueous solution.

The resulting paste is printed on linen or a nylon fabric. The material is dried for 10 minutes at 140 C. There are obtained pigment prints fast to rubbing and washing.

Example 6 56 parts of gelatine and 56 parts of urea are dissolved in 75 parts of water. The resulting solution is introduced into an apparatus provided withva very powerful stirring mechanism, and then 151 parts of the carbamide resin solution mentioned in Example 3 are run in. After the resulting emulsion has been homogenised, it is diluted With 112 parts of water, and there are then added 100 parts of a pigment preparation which contains 25 per cent. of the nely dispersed reaction product of diazotised 2-amino-5-chlorotoluene with 2:3-hydroxynaphthoic acid-4- chloro-5'-methyl-anisidide, 8 per cent. of casein, 1 per cent of borax and 3 per cent. of sodium lauryl sulfate. 25 parts of an aqueous solution of 50 per cent, strength of ammonium thiocyanate are added to the thin resin emulsion containing pigment, and then 425 parts of lacquer benzine or sangajol (boiling at 15G-210 C.) are added, and the whole is powerfully stirred until a smooth uniform paste is obtained which can easily be used for printing.

When the above paste is applied, for example, to cotton Sateen, fixed for 5 minutes at 140 C. or fixed by acid steaming at 102 C., there are obtained bright fast red prints.

What I claim is:

1. A three-phase emulsion of artificial resins, especially suitable for improving textiles, of which the external phase is a pigment-containing aqueous phase and consists of a protein solution containing at least one hydrotropic carbamide of the group consisting of urea and thiourea, of which the first internal oily phase consists of a solution, in a substantially water-immiscible alcohol of a water-insoluble hardenable condensate of formaldehyde with at least one aminoplast-forining substance selected from the group `consisting of urea, thiourea, guanidine, y

biuret, dicyandiamide and melamine and with a substantially water-immiscible alcohol, and of which the second internal oily phase consists of an inert organic water-immiscible solvent boiling not appreciably below 100 C. and not appreciably above 200 C. and which does not dissolve the water-insoluble condensate.

2. A three-phase emulsion of artificial resins, especially suitable for improving textiles, of which the external phase is a pigment-containing aqueous phase and consists of a protein solution containing at least one hydrotropic carbarnide of the group consisting of urea and thiourea, of which the first internal oily phase consists of a solution, in a substantially water-immiscible alcohol, of a water-insoluble Vhardenable condensate of formaldehyde with at least one aminoplast-forming substance of the group consisting of urea, thiourea, guanidine, biuret, dicyandiamide and melamine and With a substantially Water-immiscible alcohol, and of which the second internal oily phase consists of an inert organic Water-immiscible solvent boiling not appreciably below 100 C. and not appreciably above 200 C. and predominantly consisting of a mixture of aliphatic hydrocarbons and which does not dissolve the waterinsoluble condensate.

3. A three-phase emulsion of artificial resins, especially suitable for improving textiles, of which the external phase is a pigment-containing aqueous phase and consists of a protein solution containing at least one hydrotropic carbamide of the group consisting of urea and thiourea, of which the first internal oily phase consists of -a solution, in a substantially water-immiscible alcohol, of a water-insoluble hardenable condensate of formaldehyde with at least one aminoplast-forming substance of the group consisting of urea, thiourea, guanidine, biuret, dicyandiamide and melamine and with a substantially water-immiscible alcohol, and of which the second internal oily phase consists of an inert organic water-immiscible solvent boiling not appreciably below 100 C. and not appreciably above 200 C. and which does not dissolve the water-insoluble condensate, in which emulsion the protein is acid casein.

4. A three-phase emulsion of artificial resins, especially suitable for improving textiles, of which the external phase is a pigment-containing aqueous phase and consists of a protein solution containing at least one hydrotropic carbamide of the group consisting of urea and thiourea, of which the rst internal oily phase consists of a solution, in a substantially water-immiscible alcohol, of a water-insoluble h-ardenable condensate of formaldehyde with at least one aminoplastforming substance of the group consisting of urea, thiourea, guanidine, biuret, dicyandiamide and melamine and with a substantially waterimmiscible alcohol, and of which the second internal oily phase consists of an inert organic waterimmiscible solvent boiling not appreciably below 100 C. and not appreciably above 200 C. and predominantly consisting of a mixture of aliphatic hydrocarbons and which does not dissolve the water-insoluble condensate, in which emulsion the protein is acid casein.

LUZIUS SCHIBLER.

REFERENCES CITED The following references are of record in the le of this patent:

UNITED STATES PATENTS OTHER REFERENCES National Paint, Varnish and Lacquer Assoc. Scientific Section, Circular 7-09, p. 466.

Neuberg, Biochemische Zeitschrift, vol. 76, 1916, page 107. 

1. A THREE-PHASE EMULSION OF ARTIFICIAL RESINS, ESPECIALLY SUITABLE FOR IMPROVING TEXTILES, OF WHICH THE EXTERNAL PHASE IS A PIGMENT-CONTAINING AQUEOUS PHASE AND CONSISTS OF A POTEIN SOLUTION CONTAINING AT LEAST ONE HYDROTROPIC CARBAMIDE OF THE GROUP CONSISTING OF UREA AND THIOUREA, OF WHICH THE FIRST INTERNAL OILY PHASE CONSISTS OF A SOLUTION, IN A SUBSTANTIALLY WATER-IMMISCIBLE ALCOHOL OF A WATER-INSOLUBLE HARDENABLE CONDENSATE OF FORMALDEHYDE WITH AT LEAST ONE AMINOPLAST-FORMING SUBSTANCE SELECTED FROM THE GROUP CONSISTING OF UREA, THIOUREA, GUANIDINE, BIURET, DICYANDIAMIDE AND MELAMIDE AND WITH A SUBSTANTIALLY WATER-IMMISCIBLE ALCOHOL, AND OF WHICH THE SECOND INTERNAL OILY PHASE CONSISTS OF AN INERT ORGANIC WATER-IMMISCIBLE SOLVENT BOILING NOT APPRECIABLY BELOW 100* C. AND NOT APPRECIABLY ABOVE 200* C. AND WHICH DOES NOT DISSOLVE THE WATER-INSOLUBLE CONDENSATE. 